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Received 28 July 2007; received in revised form 28 December 2007; accepted 10 January 2008
Abstract
Renewable resource based green biocomposites were prepared using a bacterial polyester i.e., poly(hydroxybutyrate-co-valerate)
(PHBV) and natural bamboo ber. Fabrication of the biocomposites was carried out by injection molding following extrusion com-
pounding of PHBV and bamboo ber with 30 or 40 wt.% ber. The mechanical, thermo-mechanical and morphological properties of
the biocomposites were evaluated. Little variation in the thermo-mechanical and impact properties was observed when the ber content
was varied. The tensile modulus of biocomposites at 40 wt.% ber improved by 175% as compared to that of neat PHBV. The theoretical
tensile modulus of the biocomposites was calculated using Christensens equations and compared with the experimental results. It was
found to be in near approximation to the experimental data. The storage modulus was aected slightly by the variation of ber content
from 30 to 40 wt.% in biocomposites. The heat deection temperature of PHBV increased by 9 C at 40 wt.% of ber reinforcement.
Morphological aspects and thermal stability were studied using scanning electron microscopy and thermo-gravimetric analysis, respec-
tively. In addition, a comparative analysis of bamboo berPHBV with wood berPHBV biocomposites was performed. Statistical
analysis of both biocomposites was carried out by performing a two-way ANOVA on their tensile and exural moduli in order to eval-
uate the eect of ber type and content in the PHBV matrix.
2008 Elsevier Ltd. All rights reserved.
1359-835X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2008.01.004
876 S. Singh et al. / Composites: Part A 39 (2008) 875886
heated from 30 to 125 C at a heating rate of 2 C/min. 5. Results and discussions
The single cantilever mode was used to test the specimens
at amplitude of 15 lm and frequency of 1 Hz. 5.1. Tensile properties
3.2.2. Heat deection temperature (HDT) Fig. 1 shows the Youngs modulus of PHBV and its
The DMA was used to determine the HDT as per composites with bamboo ber at 30 and 40 wt.% loadings.
ASTM D648. Rectangular bars 2 12 58 mm in three- The modulus of the PHBV composites increased steadily
point bending mode with an applying load of 66 psi with ber loading. At 30 wt.% ber loading it increased
(455 KPa) were used for testing. Samples were heated at by 67% and at 40 wt.% the increase was 175%. Tensile
the rate of 2 C/min from room temperature to the temper- properties of short ber composites depend on ber length,
ature required to produce 0.195% strain. distribution, orientation and their interfacial bond strength
with matrix. The ber orientations have been assumed to
3.3. Thermal properties be random; as observed visually and composites behave
isotropically. The increased modulus of the composites
3.3.1. Thermo-gravimetric analysis (TGA) can be ascribed to uniform dispersion of bers in the
TGA was tested using TGA 2950 instrument with a PHBV matrix; which leads to the even distribution and
heating rate of 20 C/min from room temperature to transfer of stress from matrix to ber. The uniform disper-
600 C, the temperature of complete thermal degradation. sion of bers was physically visible in specimens. The ten-
All TGA runs were performed under a nitrogen purge. sile strength of PHBV decreased with the addition of
bamboo ber. This can be attributed to the lack of su-
3.3.2. Dierential scanning calorimetry (DSC) cient interfacial interaction between the ber and matrix.
DSC of the samples was performed using a model Q100 The presence of polar group on the lignocellulosic natural
DSC, TA Instruments. The heat/cool method was adopted bers and the abundant moderate polar groups in the
for all specimens testing. Specimens were heated to 190 C chemical makeup of PHBV lead to an expectation of some
at a ramp rate of 10 C/min and cooled with the same interfacial interaction between the two; although from the
ramp. The data for melting points and heat of crystalliza- FTIR analysis, no chemical or hydrogen bond interactions
tion were collected during the heating cycle. The crystalli- between the moderately polar groups of the two compo-
zation temperature and heat of fusion were obtained nents were observed. Reader may refer Fig. 7 for this pur-
from the cooling cycle. pose. Therefore, the only possible interactions responsible
Data analyses of DMA, HDT, TGA and DSC results for the load transfer from matrix to ber were frictional
were performed using the supplied software Universal and Van der Waal forces. To increase the interfacial bond-
Analysis and the numbers of specimens used for testing ing between the ber and matrix use of compatiblizer lies
each composition were three. under the scope of future work.
4. FTIR analysis
5.2. Christensens model
A PerkinElmer system 2000 FTIR Spectrometer was
used with an attenuated total reectance (ATR) accessory The theoretical Youngs modulus of the composites has
to gather the IR spectra of neat PHBV and its natural ber been estimated using Christensens model of equations
composites. [16,17]. It provides a solution for the elastic properties of
composites with randomly oriented short bers. The fol-
4.1. Morphological studies lowing expression predicts the elastic modulus of compos-
ites below and above the critical length (lc) of the ber.
Morphological studies were conducted using a JEOL
scanning electron microscope (model JSM-6400). Speci-
mens were sputter-coated with gold to a thickness of 3.5 25
10 nm before surface characterization in order to prevent
Tensile Strength (MPa)
Tensile Modulus (GPa)
3
20
charging. The SEM was equipped with a lanthanum hexab- 2.5
oride (LaB6) crystal as electron emitter source. An acceler- 2 15
0 0
Statistical analysis of tensile and exural modulus Neat PHBV 30/70 (BF/PHBV) 40/60 (BF/PHBV)
on the PHBV and its composites with wood and bamboo Fig. 1. Tensile properties of bamboo berPHBV composites at 30 and
ber at 30 and 40 wt.% using MINITAB software. 40 wt.% ber, (j) tensile modulus, () tensile strength.
878 S. Singh et al. / Composites: Part A 39 (2008) 875886
1 lc crystallinity, which had been noted from the FTIR and
E c vf E f 1 vm E m at l > lc
6 2l DSC analysis.
1 l
E c vf E f vm E m at l < lc 5.3. Flexural properties
6 2lc
Flexural modulus and strength of PHBV and its bamboo
Ec denotes the modulus of the composite, Ef and Em that of ber composites with dierent ber loadings are shown in
ber and matrix (in this case bamboo ber and PHBV), vf Fig. 3. In general, the modulus increased with incorpora-
and vm are the volume fractions of ber and matrix, respec- tion of bers. At 30 wt.% of ber content the PHBV mod-
tively, l is the ber length and lc the critical ber length ulus improved by 100% and the increase was greater at
which is given by an expression of the Rosen model. For 40 wt.% ber with the modulus jump of 154%. The exural
a bamboo ber lc < l. strength of PHBV remained unchanged upon the addition
" 1=2 # of bers. The improved exural modulus and retained
1=2
lc 1 vf Ef strength of the composites validates the reasonable amount
1:15 1=2
df vf Gm of compatibility and interfacial interaction of cellulose ber
to the natural polyester PHBV. Fiber orientation in the
d f is the diameter of the fiber
matrix plays a vital role in determining the exural proper-
ties. Unlike tensile testing (where induced tensile stress
Gm has been estimated from a general relation plays crucial role) the exural testing incorporates both
E
G m is Poissons ratio compression and tensile stresses on the ber, matrix and
21 m their interface across the specimen cross section, therefore
Fig. 2 depicts the theoretical and experimentally deter-
the strength response to the stress during exural testing
mined values of the modulus. Theoretical values of ligno-
would be higher than during tensile testing. The tensile
cellulosic natural bers (bamboo) and the PHBV matrix
strength is chiey govern by the dewetting of matrix from
have been approximated to be 25 GPa [18] and 1.02 GPa,
the ber under tensile load and also is more sensitive to
respectively. Volume fraction of the ber and the matrix
the defects originated in the interfaces of matrix and ber.
at 30 and 40 wt.% were calculated using general equations
mf
qf
vf mf and vm = (1 vf) assuming density of natural 5.4. Dynamic mechanical analysis (DMA)
mqmm qf
ber (qf) and matrix (qm) to be 0.84 gm cm3 [19] for
The viscoelastic characteristics of the materials were
bamboo ber and 1.25 gm cm3 for PHBV. The modulus
measured using DMA. It is a complex quantity dened
of bamboo berPHBV composites as predicted by
with elastic (storage) and viscous (loss) components;
Christensens model are in close approximation to the
denoted E0 and E00 , respectively. In DMA, the eect of tem-
experimental results. This was due to the uniform and nar-
perature on the viscoelastic properties of the composites
row size distribution of bamboo bers, although not quan-
was studied. This gives more distinct insight to the interac-
tied but observed visually. The dierence between the
tions at the molecular level of the materials.
theoretical and experimental data can be due to the
Fig. 4 depicts the change in the E0 of PHBV and its com-
agglomeration of the llers at high volume fractions which
posites with temperature. Like a generic tendency of ther-
results in the higher modulus than the expected. The
moplastic composites, E0 of PHBV and its composites
agglomeration was visible in SEM micro photographs.
decreases with rising temperature. E0 of PHBV increased
Although the composites have been assumed to be isotro-
with the ber loading up to 40 wt.%. The dierence between
pic; anisotropy of the bers cannot be ruled out. The model
the modulus values of bamboo ber composites at 30 and
does not account for the eect of ller and processing con-
40 wt.% was not signicant. E0 of bamboo ber composites
ditions on the matrix (PHBV), e.g., change in the degree of
3.5
Flexural Strength (MPa)
Flexural Modulus (GPa)
3.5
Elastic modulus (GPa)
3 30
3
2.5
2.5
2 20
2
1.5
1.5
1 1 10
0.5 0.5
0 0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 Neat PHBV 30/70 (BF/PHBV) 40/60 (BF/PHBV)
Volume fraction of fiber Fiber/PHBV (wt%)
Fig. 2. Experimental and theoretical data plots. h PHBVbamboo ber Fig. 3. Flexural properties of bamboo ber/PHBV composites having 30
composite, () Theoretical PHBVbamboo ber composite. and 40 wt.% ber, (j) exural modulus, () exural strength.
S. Singh et al. / Composites: Part A 39 (2008) 875886 879
7000 ness of the PHBV with the ber loading decreases the tan d
6000 peak value thus reecting the reduced energy losses in the
interfacial regions. Low dampening of the composites in
Storage Modulus (MPa)
5000 (b)
the transition region is attributed to the neness of the bam-
4000 (c) boo bers which allows their uniform distribution and crys-
3000 tallinity eect on the matrix. The widening of the tan d curve
(a) also indicates the increased heterogeneity of the specimens
2000
which was observed from the SEM photomicrographs.
1000 The maxima of the loss modulus of PHBV and its compos-
0 ites (Fig. 6) occur in the glass transition temperature region.
-25 0 25 50 75 100 125 150 The enhanced response of molecular chains to the tempera-
Temperature ( C)
ture in the amorphous region increases the viscous charac-
Fig. 4. Storage modulus versus temperature of PHBV with varying teristic of the material in the glass transition domain. The
loading level of ber (a) PHBV, (b) PHBV/bamboo ber (70:30) wt.% and ber incorporation into the PHBV slightly increases its Tg
(c) PHBV/bamboo ber (60:40) wt.%. towards higher temperature, thus delaying the increasing
viscosity component of the composites. This can be due to
improved by 157% and 173% at 30 and 40 wt.% ber con- the restriction imposed by the bers on the movement of
tent at 25 C, respectively. The increase in E0 of the ber the expanding molecular chains in the amorphous region.
lled PHBV with respect to neat PHBV was greater below
Tg than above it. This can be attributed to the temperature
sensitivity of the natural ber. The slope of the E0 versus 5.5. FTIR analysis
temperature curve around the glass transition (Tg) temper-
ature (1 C) of PHBV increases with the ber loading. In the PHBV IR spectra, Fig. 7a, the band at 1720 cm1
This gave an indication of increased brittleness of these was the C@O stretch of the ester group present in the
composites. A small bump in the curve of PHBV at 52 C molecular chain of highly ordered crystalline structure
is indicative of the cold crystallization region. During the [20]. A small hump at 1740 cm1 was of the C@O stretch
heating cycle as the specimen enters the cold crystallization in the amorphous region of semicrystalline PHBV. Charac-
region, the increasing crystallinity leads to decrease in the teristic peaks of symmetric COC stretching vibration
reduction rate of E0 as a result a small bump emerges in this were present from 800 cm1 to 975 cm1 and the antisym-
region. The cold crystallization temperature (Tcc) decreases metric COCstretching between 1060 and 1150 cm1
with ber loading. The Tcc decreases to 46 C in case of [21]. The band around 1378 cm1 corresponds to the sym-
bamboo ber composites. This could be due to very low metrical wagging of CH3 groups and at 1453 cm1 was due
diameter or high aspect ratio of the bamboo ber versus to asymmetric deformation of methylene groups, the inten-
the wood bers which gave it a better opportunity to act sity of both the peaks is independent of crystallinity or in
as nucleating agent in PHBV matrix. Among the dynamic other words insensitive to crystallinity. The absorption
mechanical properties, dampening is most sensitive to the bands at 1720, 1276, 1228, and 980 cm1 arose from the
structural heterogeneity, morphological and transitions crystalline regions (designated with arrows) and bands at
changes of system, and bermatrix interfacial interactions. 1740, 1453, 1176 cm1 from the amorphous regions (desig-
Fig. 5 shows the dampening of the PHBV and its ber com- nated with two face arrows) of PHBV. Peak at 1228 cm1
posites. Tan d expressed as the ratio of E00 to E0 gives was purely of the conformational band of crystalline helical
account of the energy dissipated as heat during the dynamic molecular chains and therefore are absent in amorphous
testing. Tan d peak occurs approximately 10 to 20 C above region [22]. The crystallinity index (CI) gives the relative
the Tg of the PHBV and its ber composites. Increased sti-
300
0.1 250
Loss Modulus (MPa)
(a)
0.08 200
Tan delta
0.04 100
(b)
0.02 50
(a)
0 0
-25 0 25 50 -25 0 25 50 75 100 125 150
Temperature (C) Temperature (C)
Fig. 5. Tan d versus temperature of PHBV with varying loading level of Fig. 6. Loss modulus versus temperature of PHBV with varying loading
ber (a) PHBV, (b) PHBV/bamboo ber (70:30) and (c) PHBV/bamboo level of ber (a) PHBV, (b) PHBV/bamboo ber (70:30) wt.% and (c)
ber (60:40). PHBV/bamboo ber (60:40) wt.%.
880 S. Singh et al. / Composites: Part A 39 (2008) 875886
(b)
(a)
Fig. 7. FTIR spectra of (a) PHBV and (b) PHBV/bamboo ber (70:30) composite.
5.6. Thermo-gravimetric analysis (TGA) ceased around 400 C. The TGA of composites also
showed the bers to be nal constituent to undergo degra-
The TGA curves in Fig. 8 depict the weight loss of dation in composites. The composite degradation maxima
bers, PHBV and its composites with temperature. Bam- occurred at temperature a little higher than that of PHBV.
boo bers began to thermally degrade at 250 C, reaching Fig. 9 illustrates the derivative weight loss of PHBV, bers
the maximum at 380 C and entirely degrading at around and their composites at 30 wt.% ber. Maximum degrada-
500 C. The PHBV lost weight gradually with the increas- tion temperature peak of the composite shifted to the
ing temperature and its thermal degradation occurred max- higher temperature from that of PHBV indicating it to be
imum at 316 C while insetting at 250 C. Its thermal a slightly more thermally stable than PHBV. Thus the pres-
instability above 250 C has earlier been reported stating ence of bamboo ber (a lignocellulosic ber) did not have
that the degradation process involves chain scission and any degradation eect on PHBV.
hydrolysis which leads to reduction in molecular weight
and formation of crotonic acid [23] and the presence of 5.7. Heat distortion temperature (HDT)
moisture further promotes hydrolytic degradation. The
thermal degradation of biocomposites appeared to be The HDT is an upper use temperature limit of a mate-
cumulative phenomena of thermal degradation of matrix rial, therefore, the eect of ber type and loading in com-
(PHBV) and ber alone. Degradation of composites initi- posites has a considerable importance in their structural
ated around 250 C in case of both, ber and PHBV and applications. The HDT of semicrystalline polymers like
S. Singh et al. / Composites: Part A 39 (2008) 875886 881
4.5 40
(a) 30
3.5
25
3
20
2.5 15
2 10
1.5 5
(b) 0
1
Neat PHBV 30/70 (BF/PHBV) 40/60 (BF/PHBV)
0.5 (c) Fiber/PHBV (wt%)
0
0 100 200 300 400 500 600
Fig. 11. Notch impact strength of PHBV/bamboo ber composites at 30
Temperature (C)
and 40 wt.% loading levels.
Fig. 9. Derivative weight loss of (a) PHBV, (b) PHBV/bamboo ber respect to ber to matrix contact, which did not allow
(70:30) and (c) bamboo ber. the sucient ber matrix interfacial interactions to
develop. As seen from the micrograph discussed in the fol-
PHBV depends on thermal history, crystallite sizes and dis- lowing section majority of the fracture occurred through
tribution along with the presence of impurities and other the ber rather than through the matrix or the interface
nucleating agents which aects their crystallinity [24]. of matrix and ber.
Fig. 10 has a description of the HDT values of PHBV
and its composites with bamboo bers at 30 and 40 wt.% 5.9. Morphology
ber content. The HDT of PHBV was enhanced by addi-
tion of bers at 30 and 40 wt.% from 114 to 120 C and Fig. 12a and b shows the micro photographs character-
123 C, respectively. The major contributing factor to the ized under SEM at dierent magnications of the impact
improved HDT with higher degree of ber content was fractured surfaces at 30 wt.% of bamboo ber composites.
the ber reinforcement which had better HDT than the
matrix. The increased storage modulus of composites at
higher temperatures also contributed to the increased
HDT. Similar types of observations have been earlier
reported [11,15].
120
HDT (C)
110
100
Neat PHBV 30/70 (BF/PHBV) 40/60 (BF/PHBV)
Fiber/PHBV (wt%)
Fig. 10. HDT of bamboo ber/PHBV composites having 30 and 40 wt.% Fig. 12. SEM photomicrographs of impact fractured samples of PHBV/
ber. bamboo (70:30) composite: (a) 90, 200 lm and (b) 450, 50 lm.
882 S. Singh et al. / Composites: Part A 39 (2008) 875886
Table 2
Description of bamboo and wooda ber based PHBV biocomposites properties
wt.% of ber in PHBV Type of Tensile properties Flexural properties Impact strength (J/mt) HDT
matrix ber (C)
Strength Modulus Strength Modulus
(MPa) (GPa) (MPa) (GPa)
0 (neat PHBV) 21.4 1.02 30.27 1.28 34.3 114
30 Bamboo 18.9 1.71 30.6 2.56 24.28 120
30 Wood 18.08 1.94 31.09 2.72 30.0 135
40 Bamboo 16.74 2.8 29.59 3.26 23.75 123
40 Wood 16.75 2.73 29.97 3.44 24.4 137
a
The data of the wood berPHBV composites has been adapted from the earlier publication of the authors for the purpose of comparison [15].
S. Singh et al. / Composites: Part A 39 (2008) 875886 883
Table 3
Description of P and F values
Tensile modulus Flexural modulus
P- F F P- F F
value critic value critic
Fiber type 0.247 1.41 4.259 0.058 3.95 4.259
Fiber loading 0 235.42 3.402 0 474.23 3.402
Interaction between 0.031 4.03 3.402 0.386 0.99 3.402
ber type and ber
loading
(b)
(c)
(a)
Heat flow down
(c)
(b)
Fig. 15. Crystallization and melting curves of (a) PHBV, (b) PHBV/bamboo ber (70:30) composite and (c) PHBV/wood ber (70:30) composite.
Table 4
boo ber to the nucleus thus decreasing the crystallinity
Detailed information obtained from dierential scanning calorimetry of
PHBV and its composites rate in case of bamboo ber composite. Similarity in the
melt crystallization peaks of PHBV and its brous compos-
Tm (C) Hf (J/g) Tc (C) Hc (J/g)
ites during cooling provided the evidence of having any
PHBV 154 57.25 101.4 48.6
divergence in their crystalline morphologies.
PHBVwood ber (70:30) 153.3 63.28 104.3 35.47
PHBVbamboo ber (70:30) 152.9 62.29 99.1 30.52 FTIR of the bamboo and wood ber were carried out to
PHBV bamboo ber (60:40) 152.7 59.44 97.2 28.92 determine an estimate of their contents and composition.
Fig. 16 shows FTIR spectra of wood and bamboo bers
(described peaks marked with arrows). The region around
of crystallization in the presence of wood ber and decrease 3400 cm1 depicted hydrogen bonded OH stretching and
in the case of bamboo ber. This may be due to slower dif- at 2900 cm1 CH stretching. The peak at 1740 cm1 was
fusion of molecular chains though the well dispersed bam- the C@O stretch in hemicelluloses present in both lignocel-
Wood fiber
A
b
s
o
r
b
Bamboo fiber
a
n
c
e
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